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Catalytic Activation of N2O at a Low-Valent Bismuth Redox Platform

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Pang,  Yue
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Leutzsch,  Markus
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Nöthling,  Nils
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Cornella,  Josep
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Pang, Y., Leutzsch, M., Nöthling, N., & Cornella, J. (2020). Catalytic Activation of N2O at a Low-Valent Bismuth Redox Platform. Journal of the American Chemical Society, 142(46), 19473-19479. doi:10.1021/jacs.0c10092.


Cite as: http://hdl.handle.net/21.11116/0000-0007-9B18-0
Abstract
Herein we present the catalytic activation of N2O at a BiI⇄BiIII redox platform. The activation of such a kinetically inert molecule was achieved by the use of bismuthinidene catalysts, aided by HBpin as reducing agent. The protocol features remarkably mild conditions (25 °C, 1 bar N2O), together with high turnover numbers (TON, up to 6700) and turnover frequencies (TOF). Analysis of the elementary steps enabled structural characterization of catalytically relevant intermediates after O-insertion, namely a rare arylbismuth oxo dimer and a unique monomeric arylbismuth hydroxide. This protocol represents a distinctive example of a main-group redox cycling for the catalytic activation of N2O.